Phenol-carbon tetrachloride beryllium halide complex



Serial No. 461,647, filed PHENOL-CARBON TETRACHLORIDE BERYLLIUM 'HALIDECOMPLEX Alvin .Guttag, Bethesda, Md.

No Drawing. Application March 13, 1958 Serial No. 721,096

8 Claims. (Cl. 260-57) This application is a continuation-impart ofapplication October 11, 1954, now 'abandoned This invention relates tothe 'reaction of phenol with carbon tetrachloride to form a complex,said complex being a new compound, and to reactmgthe complex withformaldehyde.

It is an object of this invention .to form a new solid compound byreacting phenol with carbon tetrachloride. It is another object of thisinvention to devise a novel way of preparing phenol-formaldehyde resins.

A further object is to regulate the reactlon rate in Iformingphenol-formaldehyde resins.

'sincevarious changes and modifications within the spirit and scope ofthe invention will become apparent to those skilled in the art from thisdetailed description.

It has now been found that these objects can be attained by reacting 0.3to 3.0 mols of phenol, 0.3 to 3.0 mols of carbon tetrachloride and 0.01to 0.9- mol of a beryllium halide per rnol of the lesser of the phenoland carbon tetrachloride to form a solid phenol-carbon tetrachloridecomplex. The reaction is accelerated by the use of heat and, hence, itis preferred to use temperatures between 50 C. and the boiling point.For convenience, the reaction is frequently carried out under reflux atatmospheric pressure.

The preferred catalyst is beryllium chloride, but there can also be usedberyllium bromide and beryllium iodide.

It has previously been proposed by Silber, Annales de Chimie, vol. 7,pages 182, 209 and 214, to react phenol with beryllium chloride in thepresence of a large excess of benzene or carbon tetrachloride to formthe beryllium salt of phenol in almost quantitative yields. The Silberreaction is distinct from the present invention since the carbontetrachloride is only a solvent and not a reactant in Silber. In thespecific example on page 214 of Silber he employed 500 cc. of benzenewith 12.5 grams of phenol and 5.2 grams of beryllium chloride. If 500cc. of carbon tetrachloride were substituted for the benzene in Silbersspecific example, there would be utilized 39.8 mols of carbontetrachloride per mol of phenol which is far outside the range employedin the present invention. In further comparison with Silber, it may benoted that if the reaction product in Example 2 of the presentspecification were a quantitative yield of beryllium phenate, therewould be formed 56.5 grams of product. Actually the product of Example 2weighed 130 grams and, hence, contained a large amount of carbontetrachloride (about 73.5 grams).

From the above discussion, it is evident that the proportions recited inthe instant specification are critical in order to form the complex ofthe present invention United States Patent for the phenol.

2,923,697 Patented Feb. 2, 1960 "ice containing carbon tetrachloride inexcess rather'than'torming a simple beryllium phenate.

This solid complex appears to be unique with phenol; it is not formedwhen benzene or toluene is substituted Thus, when 101.9 grams (1.31mols) of benzene were mixed with 44.1 grams (0.051 mol) of berylliumchloride and 200 cc. of carbon tetrachloride, there was no reaction,even after heating for several hours at reflux temperature.

Similarly, when 84.7 grams (1.12 mols) of toluene, 4.9 grams (0.061 mol)of beryllium chloride and 200 cc. of carbon tetrachloride were refluxedfor slightly over 2 hours, there was no reaction.

Example 1 Phenol 44.3 grams (0.471'mol). eryllium chloride 24.5 grams(0.306 mol).

cc. (0.96 mol).

Carbontetrachloride "boiling at 66 -to 11-5 C. at atmospheric pressurewas discarded. The residue was distilled at 50 mm. pressure. 'Italldistilled at 102m 104 C., atthatpressure whichshowed that it wasphenol. T he phenol and carbon tetrachloridethus combined in thepresence of the -beryl liumchloride to give-a relatively stablecomplex'which can "be brokenup slowly-in the presence ofwater or morerapidly in the presence of acid.

Example 2 Phenol 51.9 grams (0.552 mol). Beryllium chloride 22.7 grams(0.284 mol).

Carbon tetrachloride cc. (1.12 mol).

The mixture was heated with stirring during the course of hour while itcame to a boil. It was then filtered and the grayish-white solid allowedto dry. The solid weighed 130 grams. The greater part of this was placedin a dessicator where it was stable for several months. A small portionwas exposed to air and it gradually lost carbon tetrachloride and turnedpink. The grayish-white solid gave no indication of melting ordecomposing when placed in a melting point tube and heated gradually to300 C. The presence of beryllium chloride may account for this latterobservation.

The grayish-white solid phenol-carbon tetrachloride complex wasnon-crystalline and crumbled like clay when squeezed in the hand. Nophenol burns were observed when it was held for some time in the hand.

This new phenol-carbon tetrachloride complex has a. number of uses.Thus, it can be used as a source of phenol wherever it is desired tocontrol a reaction in which phenol reacts violently. As the break-up ofthe complex is gradual, the reaction of phenol with the other reactantcan readily be controlled. Thus, for example, 100 grams of the complex(containing 28.5 grams of phenol) was reacted with 25 cc. of 40%formalin at reilux temperature for 60 minutes to give a novolak. Thecarbon tetrachloride and water were removed by distillation in a vacuum(water pump) until the temperature of the mixture reached 90 C. Thenovolak can then be mixed with wood flour and sufiicient hexamethylenetetramine to give an excess of formaldehyde to cure the novolak in theusual way. Instead of formalin, if a slower reaction rate is desired,neutral aqueous formaldehyde can be used. The water present aids in thebreakup of the complex and the gradual release of hydrochloric acidthrough hydrolysis of the beryllium chloride in the complex. Theberyllium chloride in the complex thus acts as a latent catalyst. If itis desired to speed up the reaction by breaking the complex morerapidly, this can be accomplished by adding a strong acid, such ashydrochloric acid or sulfuric acid'in varying amounts, depending on thespeed with which it is desired to break up the complex.

Conventional thermosetting resins can also be made by adding an excessof formaldehyde and alkaline catalyst. In this case, insoluble berylliumhydroxide will form and it can be left in the resin as a filler.

I claim:

1. A solid complex reaction product prepared by condensing at atemperature of between 50 C. and the boiling point 0.3 to 3.0 mols ofphenol, 0.3 to 3.0 mols of carbon tetrachloride and 0.01 to 0.9 mol ofberyllium chloride per mol of the lesser of the phenol and carbontetrachloride, said reaction product being characterized by beingcapable of decomposing to reform the phenol, carbon tetrachloride andhydrolysis products ofberyllium chloride in the presence of water andaqueous acid.

2. The process comprising reacting at a temperature of between 50 C. andthe boiling point 0.3 to 3.0 mols of phenol, 0.3 to 3.0 mols of carbontetrachloride and 0.01 to 0.9 mol of a beryllium halide per mol of thelesser of the phenol and the carbon tetrachloride to form a solidcomplex reaction product, said reaction product being capable ofdecomposing to reform the phenol, carbon tetrachloride and hydrolysisproducts of beryllium halide in the presence of water and aqueous acid.

3. The process comprising reacting a solid phenol-carbontetrachloride-beryllium chloride complex made by heating at atemperature from 50 C. to the boiling point 0.3 to 3.0 mols of phenol,0.3 to 3.0 mols of carbon tetrachloride and 0.01 to 0.9 mol of berylliumchloride per mol of the lesser of the phenol and carbon tetrachloridewith aqueous formaldehyde to form a phenolformaldehyde resin, saidphenol being phenol per se.

4. A solid complex reaction product made by condensing at a temperatureof between 50 chloride up to 3 mols per mol of phenol.

5. A process according to claim 2 including the additional step ofreacting the phenol-carbon tetrachlorideberyllium halide complex withaqueousformaldehyde to form a phenol-formaldehyde resin, ma phenol beingphenol perse.

6. A process according to claim lium halide is beryllium chloride.

7. A solid complex reaction product'prepared by condensing at atemperature of between 50 C. and the boiling point 0.3 to 3.0 mols ofphenol, 0.3 to 3.0 mols of carbon tetrachloride and 0.01 to 0.9 mol of aberyllium halide per mol of the lesser of the phenol and carbontetrachloride. I

8. A solid complex reaction product prepared by condensing at atemperature of between 50 C. and the boiling point 0.552 mol of phenol,0.284 mol of beryllium 25 chloride and 1.12 mol of carbon tetrachloride.

v 2 wherein the beryl- References Cited in the file of this patentUNITED STATES PATENTS 2,171,207 Boultbee Aug. 29, 1939 2,222,012 Amos eta1 Nov. 19, 1940 2,835,714 Nixon et al. May 20, 1958 OTHER REFERENCESSilber: Annales de Chirnic, vol. 7 (1952), pages 182 and 209. Chatfield:Varnish Constituents, Leonard Hill, London (1953), pages 292-295.

0 Merck Index, 6th ed., 1952, page 109, Merck & Co.,

2. THE PROCESS COMPRISING REACTING AT A TEMPERATURE OF BETWEEN 50*C. ANDTHE BOILING POINT 0.3 TO 3.0 MOLS OF PHENOL, 0.3 TO 3.3 MOLS OF CARBONTETRACHLORIDE AND 0.01 TO 0.9 MOL OF A BERYLLIUM HALIDE PER MOL OF THELESSER OF THE PHONEL AND THE CARBON TETRACHLORIDE TO FORM A SOLIDCOMPLEX REACTION PRODUCT, SAID REACTION PRODUCT BEING CAPABLE OFDECOMPOSING TO REFORM THE PHENOL-CARBON TETRACHLORIDE AND HYDROLYSISPRODUCTS OF BERYLLIUM HALIDE IN THE PRESENCE OF WATER AND AQUEOUS ACID.3. THE PROCESS COMPRISING REACTING A SOLID PHENOL-CARBONTETRACHLORIDE-BERYLLIUM CHLORIDE COMPLEX MADE BY HEATING AT ATEMPERATURE FROM 50*C. TO THE BOILING POINT 0.3 TO 3.0 MOLS OF PHENOL,0.3 TO 3.0 MOLS OF CARBON TETRACHLORIDE AND 0.01 TO 09 MOL OF BERYLLIUMCHLORIDE PER MOLS OF THE LESSER OF THE PHENOL AND CARBON TETRACHLORIDEWITH AQUEOUS FORMALDEHYDE TO FORM A PHENOLFORMALDEHYDE RESIN, SAIDPHENOL BEING PHENOL PER SE.